EP2782549B1 - Antimikrobielle konservierungszusammensetzungen für körperpflegeprodukte - Google Patents

Antimikrobielle konservierungszusammensetzungen für körperpflegeprodukte Download PDF

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EP2782549B1
EP2782549B1 EP12806160.3A EP12806160A EP2782549B1 EP 2782549 B1 EP2782549 B1 EP 2782549B1 EP 12806160 A EP12806160 A EP 12806160A EP 2782549 B1 EP2782549 B1 EP 2782549B1
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personal care
preservative composition
weight
component
antimicrobial
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EP2782549A2 (de
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Nirmal Koshti
Shraddha Kiran RATNAPARKHE
Devyani Ashok MALI
Bhagyesh Sawant
Pooja Dinkar VAIDYA
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Galaxy Surfactants Ltd
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Galaxy Surfactants Ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/592—Mixtures of compounds complementing their respective functions
    • A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations

Definitions

  • the present invention relates to the preservation of personal care formulations with synergistic blends of three types of ingredients that offer a broad spectrum of activity against the microbes namely, an undecylenic acid derivative of Formula (I), an octanoic acid component of Formula (II) and 2-phenoxy ethanol. Further, the invention relates to a personal care formulation comprising the above blends of three types of ingredients.
  • the most effective antimicrobials that are used for creating these combinations for topical personal care products can be classified into four major categories.
  • the four categories are 1) phenolic antimicrobials 2) formaldehyde releasing compounds 3) quaternary ammonium compounds and 4) halogenated antimicrobials.
  • the examples of phenolic compounds are parabens and the examples of phenolic halogenated compounds are, Triclosan and chloroxylenol. Chloroxylenol is significantly toxic to mammals and is a skin irritant with quite allergic properties.
  • the examples of nonphenolic halogenated compounds are 2-bromo-2-nitro-1, 3 propane diol, and chloroisothiazolinone.
  • formaldehyde releasing compounds are DMDM hydantoin, diimidazolidinyl urea and examples of quaternary ammonium compounds are benzethonium chloride and cetyl pyridinium chloride.
  • Parabens are esters of p -hydroxy benzoic acid. Some parabens are active against bacteria and some show activity against fungi. Usually they are used in combination of at least two or in most cases combination of 4 to 5. In fact all five (methyl, ethyl, propyl, butyl and isobutyl) parabens are often times combined with other antimicrobial to seek lower dosage and synergy in the antimicrobial efficacy. For example, Clariant's 'Phenonip' is a blend of six antimicrobials out of which the five are parabens. The same company offers blends of only parabens as 'Nipastat' and 'Nipasept'.
  • Elestab FL 15 Elestab 48, Elestab 50J, Elestab 305, Elestab 388, Elestab 3344, Elestab 4112, Elestab 4121, Elestab 4150 Lipo are all blends of antimicrobials with at least one paraben in them.
  • Galaxy Surfactants offers Galguard NK1 and Galguard NK2 blends that are based on four and five paraben blends respectively with 2-phenoxy ethanol. Five blends by McIntyre/Rhodia from their 'Paragon' series have several parabens.
  • Neolone MXP of Rohm and Haas has parabens with methyl isothiazolinone.
  • Neo-Dragocide series of blends from Symrise has parabens.
  • Euxyl K 300 of Schulke and Mayr has five parabens.
  • Thor's Microcare PM4 and Microcare PM5 have four and five parabens respectively. What it shows is that the parabens are doing a great job of being good preservatives.
  • Formaldehyde releasing antimicrobials Formaldehyde is classified as Category 3 CMR (carcinogenic, mutagenic and reproductive toxicity). However, it is interesting to note that a few antimicrobials that slowly release formaldehyde are still being used and being commercially manufactured. Due to the paucity of effective and well-accepted antimicrobials, the industry is forced to continue with the using formaldehyde donors like DMDM hydantoin, imidazolidinyl urea, and diazolidinyl urea. The formaldehyde released by these substances is capable of reacting with several cosmetic ingredients via its very reactive aldehydic carbonyl functionality.
  • UV-A absorber Avobenzone
  • formaldehyde that is released by formaldehyde derivatives.
  • This is a big disadvantage for sunscreen formulations.
  • Preservative blends Clariant's Niapaguard PDU and Cognis's Elestab 305
  • ISP's Germaben II, Germaben H-E exploit combinations of parabens with diazolidinyl urea.
  • ISP's Germall Plus and Lonza's Glydant Plus have diazolidinyl urea along with iodopropynyl butyl carbamate (IPBC) in them.
  • IPBC iodopropynyl butyl carbamate
  • McIntyre's Paragon series has DMDM hydantoin and other antimicrobials like paraben, phenoxy ethanol and IPBC. Symrise's Neo-Dragocide and Thor's Microcare IMP exploit synergy between parabens and imidazolidinyl urea.
  • Quaternary ammonium antimicrobials The third category of the quaternary ammonium compounds (examples are cetyl pyridinium chloride, benzethonium chloride, benzalkonium chloride, polyaminopropyl biguanide), has been of limited use for personal care industry due to specific incompatibilities with other cosmetic ingredients.
  • Geogard 233S Geogard 233S, Geogard 233S, Geogard 361
  • these antimicrobial compositions are based on cationic benzethonium chloride which gets deactivated by many anionic ingredients that form important part of topical personal care formulations.
  • Halogentated antimicrobials Nalco's Merguard series (four blends) banks on halogenated molecules, methyl dirbromo glutaronitrile and 2-bromo-2-nitro-1,3-diol.
  • Several blends of Euxyl series from Schulke and Mayr are based on chlorothiazolinones, methyl dibromo glutaronitrile, 2-bromo-2-nitro-1,3-diol and diazolidinyl urea.
  • Microcare series from Thor employs parabens, 2-bromo-2-nitro-1,3-diol, iodopropynyl butylcarbamate (IPBC), imidazolidynyl urea, and diazolidinyl urea.
  • IPBC iodopropynyl butylcarbamate
  • halogenated antimicrobials are chlorphenesin, and chlorhexidine. It is common knowledge that like phenolic compounds, the halogenated organic molecules exhibit significant levels of toxic effects. For example, IPBC has risk of thyroid hormonal disturbances due to its iodine content. It has not been allowed in Japan and in EU it is allowed only up to 0.02 % in leave-on products. Similarly EU permits usage of methyl dirbromo glutaronitrile only up to 0.1 % and that too in only rinse-off products. Bronopol, 2-bromo-2-nitropropane-1, 3-diol, is implicated in generation of carcinogenic nitrosoamines on interacting with some of the nitrogen containing cosmetic ingredients.
  • Methyl chloro isothiazolinone is so powerful antimicrobial that it is allowed only in rinse-off products at 15 ppm concentration. Chloromethyl isothiazolinone does have a very broad spectrum of anti-microbial activity. But the toxicity of such powerful anti-microbials is extremely high and hence cosmetic formulators do not prefer to use this kind of powerful antimicrobial in the cosmetics that remain on human skin for a long time. It is reasonable to expect that any thing that is strong bactericidal at a low concentration (ppm level) is likely to be equally lethal to any other cells of a living organism, including human cells. This is the precise reason why in Japan chloromethyl isothiazolinone is not allowed for preservation if the product is going to come in contact with the mucous membrane.
  • MicroKill COS and MicroKill PCC that are based on chlorphenesin and chloroxylenol respectively. It is to be noted that these preservatives are free from parabens and free from formaldehyde releasers but they are halogenated molecules.
  • Lonza's recent commercial introductions commercial are Geogard 2333, Geogard 2355, and Geogard 361 are based on benzethonium chloride, a quaternary ammonium compound.
  • ISP's latest invention is Liquagard which is nothing but iodopropynyl butyl carbamate (IPBC), again a halogenated molecule.
  • Vertellus Specialities, Italy launched ZeStat that is again a quaternary ammonium surfactant, cetyl pyridinium chloride.
  • US 5736574 A teaches certain combinatory antimicrobial immixtures comprising at least one antimicrobial hydrolipid and/or lipid and an antimicrobially synergistically effective amount of at least one glyceryl monoalkyl ether.
  • Undecylenic acid derivatives are mentioned as hydrolipids and
  • a combinatory immixture of N-n-Octanoylglycine and 1-(2-ethylhexyl) glyceryl ether is disclosed.
  • WO 2007/104879 A2 teaches powder composition of n-acylated amino acids, and use thereof for preparing cosmetic and/or pharmaceutical formulations.
  • N undecylenoyl glycine is disclosed as part of the compositions taught in WO 2007/104879 A2 .
  • composition D discloses a premix comprising before impregnation on the porous particles 7% undecylenoyl glycine and 8% octanoyl glycine dissolved in glycerine.
  • Octiphen BSB-N from ISP is a combination of benzoic acid, sorbic acid and benzyl alcohol.
  • Sharon MX 705 is a blend of sorbic acid, benzyl alcohol, benzoic acid and dehydroacetic acid.
  • the antimicrobial manufacturers do not seem to be looking to invent the 'ideal' preservative but synergistic combinations of antimicrobials to avoid parabens or formaldehyde donors.
  • the combination of organic acids are being used.
  • a limitation of low molecular weight organic acids is that they are effective in acid form and hence only at low pH show efficacy as antimicrobial preservative.
  • benzoic acid is effective if it remains as benzoic acid and loses it efficacy in its 'benzoate' form.
  • undecylenic acid derivatives have been reported to possess some antifungal activity, these have not been exploited commercially for the preservation of personal care formulations.
  • undecylenoyl glycine is reported to possess anti-acne activity, ( CAS No 54301-26-7 , EINECS No 427-430-5) when used along with other ingredients like zinc gluconate, capryloyl glycine, plant extracts from rathania, tea, cinnamon, willows or hamemelis ( EP 0983055131 ).
  • the significant limitation of using lipidated amino acid like undecylenoyl glycine is that they show effectiveness only when present in carboxylic acid form.
  • the present invention overcomes this limitation by creating preservative systems that have antimicrobial undecylenoyl derivative that remains active over a broad pH range.
  • the present invention thus provides a preservative combination made up of very 'safe and nontoxic' personal care ingredients and that are free from parabens, formaldehyde donors, phenolic compounds, halogenated molecules and quaternary ammonium molecules.
  • It is an object of the present invention is to overcome the drawbacks of the prior art.
  • Yet another object of present invention is to provide an economic and cost effective preservation system.
  • the present invention provides a synergistic combination of cosmetic ingredients comprising a) non-phenolic, b) non-halogenated and c) non-formaldehyde releasers to preserve personal care formulations. All the components of the combination are safe and completely biodegradable substances that are widely used by personal care industry.
  • the inventors of present invention have found that the combination of preservation system shows synergistic effect in terms of the antimicrobial effect even at lower concentration in comparison with the individual substances.
  • the present invention provides novel combinations of surfactants with undecylenic chain as the hydrophobe (Formula I) and surfactants with octanoyl chain (Formula II) as the hydrophobe along with a 'liquid alcohol ether', namely 2-phenoxy ethanol.
  • the hydrophobic portion is provided by octanoyl (C8) and undecylenoyl (C10) chains and the hydrophilic portion is provided by hydroxylgroups .
  • Suitable concentration of the 'three component' preservative systems of the present invention may vary according to the personal care product formulation that is being preserved depending upon the amount of water in the formulation. It varies from 0.5 % to 2.5 % by weight of the total topical formulation.
  • the MICs (minimum inhibitory concentration) against a variety of microbes for the 'three component' blend is lower than the individual constituents.
  • the antimicrobial efficacy of their preservative blends was 'challenge tested' through a variety of formulations and against a variety of microbes to determine the efficacy of the blends.
  • present invention teaches use of one or more undecylenic acid derivatives (Formula I), component [A], as one of the three components of the preservative system.
  • undecylenic acid derivatives Component [A]
  • component [A] component [A]
  • cosmetic ingredients derived from undecylenic acid that are commercially available.
  • undecylenoyl derivatives are being used as cosmetic biocide, foam booster, viscosity booster, conditioner, anti-dandruff, and in antifungal applications in foot powder and underarm deodorant stick.
  • the personal care ingredients based on undecylenic acid listed in the International Cosmetic Ingredient Directory and Handbook are undecylenlamide MEA and undecylenlamide DEA, undecylenoyl MEA sulphosuccinate, undecylenoyl amidopropyl betaine, glucosyl undecylenate, undecylenoyl PEG-5 paraben (antimicrobial), undecylenoyl phenylalanine (skin conditioning agent), undecylenoyl serine/silk amino acid methyl ester(hair skin and nail conditioning agent), undecylenoyl wheat amino acid (surfactant), undecylenoyl collagen amino acid, undecylenamidoproppyl trimonium methosulphate (antistatic hair conditioner), undecylenamidopropyl amine oxide (cleansing agent, foam booster), undecylenamidopropyl betaine (fo
  • the present invention provides a preservative system that is based on undecylenoyl derivatives that are not affected by the variation in the pH.
  • the examples of such undecylenic derivatives are the alkanol amides of undecylenic acid.
  • Alkanolamides of undecylenic acids are non-ionic surfactants that have disinfecting properties ( HU 9800933A2 ).
  • Undecylenoyl monoethanol amide ( CAS 20545-92-0 ) is used in several topical applications that deal with fungal infection of skin (Cosmetologic de Harry by J.B. Wilkinson, R. J. Moore, Marta Rodriguez Navarro). Commercially, it is available by the trade name of Fungicid UMA from Dragacco.
  • Undecylenoyl diethanol amide ( CAS No 60239-68-1 ) is commercially available as Rewocid DU 185SE from Evonik-Goldschmidt (Handbook of preservatives by Michael Ash and Irene Ash, 2004).
  • the disodium undecylenaamido MEA sulphosuccinate an anionic surfactant, also shows phenomenal anti-microbial activity.
  • US Patent No 3,385,755 reports marked antifungal activity of this sulphosuccinate surfactant of undecylenic acid along with others particularly against Tricophytum mentagrophytis and Pityrosporum ovale .
  • Rewocid SBU from Evonik-Goldschmidt.
  • undecylenamidopropyl trimonium methosulphate a quaternary ammonium surfactant, commercially available as Rewocid UTM 185, exhibits powerful antifungal activity.
  • Undecylenic component, component [A] of Formula (I) is selected at least from undecylenic monoethanol amide.
  • the second component, [B], in these 'three component' preservative systems of the present invention is the N -octanoyl derivative of Formula II. They are mainly two types of non-ionic surfactants N -octanoyl alkanol amides and N -octanoyl glycine.
  • N -octanoyl MEA amide (CAS No 7112-02-9 , N -(2-hydroxylethyl)caprylic acid amide) is very much the part of cocomono ethanol amide ( CAS 681-40-001 , EINECS No 268-770-2) and cocodiethanol amide ( CAS No 68603-42-9 , EINECS No 271-657-0) that are used by the personal industry on a huge scale for viscosity build up or as a rheology modifier.
  • These alkanol amides are mixtures of alkanol amides with hydrophobic alkyl chain ranging from C8 to C18, derived from coconut or palm kernel fatty acids.
  • C 8 and C 10 based alkanol amides in commercially available coco-fatty acid based alkanol amide range from 4 % to 12 %. This is the percentage range these occur in nature in coconut oil or palm kernel oil.
  • N -octanoyl MEA amide is a surface active agent and reduces surface tension of water to 30 dynes/cm at 0.1 % concentration. Its synthesis was first reported by D'Alelio, G.F.; Reid, and E. Emmet in Journal of the American Chemical Society (1937 ).
  • N -Octanoyl glycine (CAS No14246-53-8 ) is again a well-accepted and well-known skin purifier/protector. Commercially, it is available as Lipacide C8G from SEPPIC, France. It is active against most of the natural resident micro-flora that reside on human skin and is used in anti-acne, antiperspirant and deodorant preparations. (Table I).
  • each of these two components [A] and [B] is present from 5 to 20 % by weight, preferably in the range of 10 to 20 %, by weight, of the total composition.
  • the third constituent [C], the liquid alcohol ether comprises 2-phenoxy ethanol.
  • the 'liquid ether alcohol' is employed with N -octanoyl component [B] and an undecylenic acid component [A].
  • the third constituent [C] is present from 70 to 90 %, preferably, 70 to 80 %, of the total preservative composition.
  • Alcohol ethers are colorless, non-volatile liquids that have very good solvent properties.
  • the component [C] that is used in the preservative blends of the present application comprises 2-Phenoxy ethanol. It occurs in the nature (Chinese Green Tea) and has been consumed by human race for centuries. 2-Phenoxy ethanol ( CAS No 122-9-6 , EC No: 204-589-7) was used as anti-microbial to treat the open wounds of soldiers in World War II. It is a gentle antimicrobial and is preferred in preserving vaccines that contain very labile proteins. 2-Phenoxy ethanol is active against Gram negative bacteria ( Cosmetic and Drug Preservation, Principles and Practice, Vol I, Ed Jon Kabara, Marcel Dekker ), however, it shows very weak activity against Gram positive and virtually no activity against fungi. However, in the synergistic formulation of the present invention the broad protection can be easily achieved by mixing the above mentioned three constituents in the right proportion.
  • the 'three component' blends of this patent application are based on well accepted, safe, cosmetic ingredients that boost each other's potency synergistically. These are designed to be economical and offer broad spectrum of activity and are easy to incorporate and their antimicrobial efficacy has been established by MICs, Time Kill Study and challenge tests performed on the various personal care formulations by introducing fresh inoculums of microbes.
  • the personal care products that are protected from the microbial contamination by the synergistic three component systems can be of any type of such as emulsions, gels, serums, solutions, toners, lotions, creams, spray, gel, powder, stick and cleansers for topical application.
  • the topical formulations according to the present invention may additionally contain further ingredients or additives such as solvents, surfactants, emulsifiers, rheology modifiers, conditioners, emollients, skin caring ingredients, other preservatives, thickeners, lubricants, fillers, antioxidants, other preservatives, active ingredients, in particular dermatologically active ingredients, fragrances and the like as well as mixtures thereof.
  • further ingredients or additives such as solvents, surfactants, emulsifiers, rheology modifiers, conditioners, emollients, skin caring ingredients, other preservatives, thickeners, lubricants, fillers, antioxidants, other preservatives, active ingredients, in particular dermatologically active ingredients, fragrances and the like as well as mixtures thereof.
  • Suitable concentration of the 'three component' systems of the present invention may vary according to the personal care product formulation that is being preserved depending upon the ingredients used and the amount of water in the formulation. It varies from 0.5 % to 2.5 % by weight of the total topical formulation.
  • 2-Phenoxy ethanol was obtained from Galaxy Surfactants Ltd, Mumbai, India.
  • 2-Ethyl hexyl glycerol (3-(2-ethyl hexyl) oxy 1, 2-propanediol, trade name Sensiva SC-50) was procured from Schulke and Mayr, Germany.
  • Undecylenic acid and octanoic acids were obtained from VVF Ltd, India. All other chemicals were purchased from Aldrich.
  • N -undecylenoyl monoethanol amide, N -octanoyl glycine, and N- octanoyl monoethanol amide were synthesized in according to the procedures given below.
  • a mixture of undecylenic acid (500g, 2.71mol) and monoethanol amine (166g, 2.71mol) is stirred under nitrogen blanket in pressure vessel at 140°C for 4 hr and then the temperature is raised to 165°C for additional one hour. At this stage, acid value is normally found to be around 10°C or less. Cool the reaction mass to 60°C and the molten mass are converted into off white flakes (610 g, 99 %) by pouring it on glass plate. (Melting point 56-58 °C, acid value, less than 10, IR (KBr):1640 cm -1 carbonyl amide ,1556 cm -1 , 2919 cm -1 , 3289 cm -1 (NH of amide).
  • a mixture of octanoic acid (114 g, 0.1 mol), BHT (0.3 g) and monoethanol amine (61 g, 0.1 mol) is stirred under nitrogen blanket in a pressure vessel at 140°C for 4 hr and then the temperature is raised to 165°C for additional one hour. At this stage, acid value is normally found to be around 5 or less.
  • the reaction was then cooled under mild vacuum to 60°C and the molten mass is converted into off-white flakes (148 g, 95 %) by pouring it on a glass plate.
  • N -octanoyl chloride 300 g, 1.84 mol
  • sodium hydroxide 319 gm, 3.88 mole
  • the reaction mass is stirred for additional one hour. It is then acidified with hydrochloric acid and cooled to 20°C.
  • N -Octanoyl glycine separates as white solid that is filtered and washed with copious amount of water to free it from mineral acidity.
  • the said compound is not reported to possess any activity against both Gram positive and Gram negative bacteria.
  • the compound does not exhibit any antimicrobial activity, neither against bacteria nor against yeast and mould up to 1.0 % concentration.
  • MIC numbers against eight microbes are given in Table I.
  • Preservative Blend No 1 A combination of N-undecylenoyl MEA amide, component [A] and N-octanoyl glycine, component [B] and 2-phenoxy ethanol, component [C] in the ratio of 10:10:80 by weight ([A]:[B]:[C] :: 10:10:80) as given in Preservative Blend No 1 (the experimental section) showed remarkable broad range of activity against all types of microbes including dandruff causing Malassezia and acne causing Propionibacterium. 2-Phenoxy ethanol by itself has virtually no activity against Aspergillus and Candida, however, in combination with component [A] and [B] of the Preservative Blend No 1, in around 0.25 % is enough to kill both organisms.
  • N-Undecylenoyl MEA amide that shows no activity by itself up 10000 ppm concentration, however, in the synergistic Preservative Blend No 1, it is effective at 200 to 300 ppm to cover a broad range of microbes.
  • the other surfactant N-octanoyl glycine too.
  • N- octanoyl glycine needs to be present in 3000 to 4000 ppm concentration to exhibit a decent level of antimicrobial activity but in a combination a mere 200 to 300 ppm concentration, almost one tenth of the concentration of an individual ingredient is required to be effective as represented in Table III.
  • Preservative blends having both amide of octanoic acid or undecylenic acid can be made in one pot synthesis. More or less similar results were obtained with Preservative Blend No 3 where the ratio on % weight basis was varied compared to Preservative Blend No 2 as shown in Table IV.
  • binary mixtures 30 % of N-undecylenoyl MEA amide and 70 % of 2-phenoxy ethanol or 30% of N-octanoyl MEA amide with 70 % of 2-phenoxy ethanol showed significantly inferior performance in terms of Minimum inhibitory concentration against the chosen eight organisms compared to the ternary mixture, the 'three component' system of Preservative Blend No 2.
  • Preservative blend No. 3 was compared with Preservative blend No. 2 based on percent weight ratio as shown in Table IV.
  • the three component systems exhibit optimum broad spectrum performance when the undecylenoyl component [A], octanoyl component [B] and the liquid alcohol ether [C] are present in a certain ratio.
  • the maximum performance was obtained when [A] and [B] are present in the range of 5 to 20 % by weight individually and together they should be present at 10 to 30 % by weight in the final preservative blend. This can be seen from the results depicted in Table IV.
  • Preservative Blend No 4 comprises both components [A] and [B] present in 8% by weight and component [C] is present in 92 % by weight. Compared to individual constituents there is still 'three component' synergistic effect. However, when performance of Blend No 4 was compared with Blend No 2 and 3, it was observed that MIC values against bacteria ( Bacillus , Staphylococcus ) and the fungi ( Aspergillus , Candida ) are quite inferior. The minimum inhibitory concentration required to restrict growth of Bacillus subtilis was found to be 7000 ppm compared to 2000 ppm of Blend No 2 and in case of Aspergillus the MIC was found to be 7000 ppm as compared to 2000 ppm for Blend No 2.
  • Blend No 5 the component [A] and [B] are present in significantly high of 25 % by weight individually, and component [C] is present at 50 % by weight.
  • component [C] is present at 50 % by weight.
  • the 'three component' synergy exists, it is far inferior to Blend No 1 and Blend No 2 (Table IV).
  • Table IV the 'maximum synergy' is obtained with certain range of individual components for the 'optimum antimicrobial broad spectrum effect'
  • Table V represents the results of Preservative Blend No 1.
  • the study was carried with 1 % Preservative Blend No 1 in 0.25% gelatine solutions.
  • the initial inoculation level of microbes for this study was 10 4 to 10 10 cfu / ml. From the Table V it can be seen that both Gram negative and Gram negative bacteria were killed in less than 10 minutes. This also includes Pseudomonas that is dreaded as the nemesis of personal care and pharmaceutical industry. It is important to see that Bacillus subtilis, tough Gram positive bacteria to destroy due to its endosperm protection, was killed within minutes.
  • the efficacy of these 'three component' blends was ascertained by performing the challenge tests on the various types of topical personal care formulations viz, a sunscreen cream formulation with SPF 15, W/O cold cream, a face wash, a shampoo formulation, shaving gel and a protein solution that were preserved with 0.4 to 1.0 % of the Preservative Blend No 1 and No 2 as exemplified below in the experimental section.
  • Protein hydrolyzate solution was selected since the hydrolyzed proteins (20%) and water form the most supporting environment for the microbes to grow.
  • the protein solution was preserved with 1.0 % of Preservative Blend No 1 and challenge tested.
  • the challenge tests were performed according CTFA guideline (Evaluation of preservatives to protect cosmetics' by D.
  • Table VI Challenge Test performed on Sunscreen Cream formulation preserved with 1.0 % Preservative Blend No 1 TVC (cfu/gm) Staphylococcus aureus ATCC 6538 S Escherichia coli ATCC 10142 Pseudomonas aeruginosa Immuno type IV Bacillus subtilis ATCC 9372 Candida albicans ATCC 10231 Aspergillus niger ATCC 16404 0 hr 35.35 ⁇ 10 5 3 ⁇ 10 9 3 ⁇ 10 9 3 ⁇ 10 9 1.05 ⁇ 10 6 11.05 ⁇ 10 6 24 hr 3.33 ⁇ 10 5 ⁇ 10 ⁇ 10 14.61 ⁇ 10 4 0.8 ⁇ 10 2 6 ⁇ 10 5 48 hr 10.9 ⁇ 10 3 ⁇ 10 ⁇ 10 28 ⁇ 10 3 ⁇ 10 14.9 ⁇ 10 5 7 days ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 14 days ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 21 days ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10 ⁇ 10
  • a shampoo, a sunscreen cream , a w/o cold cream, a shaving gel and a face wash were prepared according to the following procedures and preserved with 0.4 to 1.0 % levels of the Preservative Blend No 1.
  • the formulations were then tested for the stability and subsequently 'challenge tested' according to CTFA guidelines.
  • the challenge test results of some of the formulations are provided in the description of the invention.
  • Components Trade Name % W/W) Phase A Water (Aqua) D. M.
  • Example 4d Preparation of a cold cream
  • HEC hydroxyethyl cellulose

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Claims (8)

  1. Eine antimikrobielle Konservierungszusammensetzung zur Konservierung topischer Körperpflegeformulierungen, umfassend
    [A] ein oder mehrere Undecylensäure-Derivate, dargestellt mit Formel (I), wobei
    M =
    NH-CH2-OH,
    NH-CH2CH2-OH,
    N-(CH2CH2-OH)2,
    NHCH2CH2CH2N(CH3)2,
    NHCH2CH2CH2N(CH3)2→O,
    NHCH2CH2CH2N+(CH3)3(CH3SO4 -),
    NHCH2CH2CH2N+(CH3)2CH2CH2N+(CH3)2CH2COO-,
    NHCH2CH2CH2N+(CH3)2CH2(OH)CH2CH2SO2O-,
    OCOR', wobei R' = C1-C18-Alkylgruppe,
    O-CH2CH2-OH,
    O-CH(OH)CH2-OH,
    O-Polyol,
    O-CH2CH2-OR', wobei R' = Undecylenoyl,
    O-C(CH3)2-OH,
    Protein-(tierisches oder pflanzliches)-Hydrolysat (über Stickstoffende), NH-CH2CH2-O-(-O-CH2CH2-)n-CO(CH)-COONa)-CH2-(SO3Na), wobei n = 0 bis 3
    Figure imgb0007
    [B] ein oder mehrere Octansäure-Derivate, dargestellt mit Formel (II), wobei
    M = NH-CH2-OH, NH-CH2CH2-OH, N(CH2CH2-OH)2 oder NH-CH2-COOH;
    Figure imgb0008
     und
    [C] 2-Phenoxyethanol oder 2-Ethylhexylglycerylether oder ein Gemisch dieser beiden flüssigen Alkoholether;
    wobei jede der beiden Komponenten [A] und [B] im Bereich von 5 bis 20 Gew.-% vorliegt und [A] und [B] gemeinsam 10 bis 30 Gew.-% ausmachen und die flüssige Alkoholether-Komponente [C] mit 70 bis 90 Gew.-% der Konservierungsgesamtzusammensetzung vorliegt,
    dadurch gekennzeichnet, dass die antimikrobielle Konservierungszusammensetzung umfasst
    [A] ein oder mehrere Undecylensäure-Derivate, dargestellt mit Formel (I), wobei
    M =
    NH-CH2CH2-OH,
    Figure imgb0009
     und
    [C] 2-Phenoxyethanol.
  2. Die antimikrobielle Konservierungszusammensetzung nach Anspruch 1, wobei besagte Dreikomponenten-Konservierungszusammensetzung ein Gemisch umfasst aus
    [A] N-Undecylenoylmonoethanolamid,
    [B] N-Octanoylmonoethanolamid, und
    [C] 2-Phenoxyethanol,
    und wobei [A] und [B] zusammen 20 Gew.-% der Konservierungszusammensetzung bilden und [C] 80 Gew.-% der Konservierungszusammensetzung darstellt.
  3. Die antimikrobielle Konservierungszusammensetzung nach Anspruch 1, wobei die Dreikomponenten-Konservierungszusammensetzung aus antimikrobiellen Mitteln für Körperpflegeformulierungen ein Gemisch umfasst aus
    [A] N-Undecylenoylmonoethanolamid,
    [B] N-Octanoylglycin, und
    [C] 2-Phenoxyethanol,
    wobei [A] mit 20 Gew.-% und [B] mit 10 Gew.-% der Konservierungszusammensetzung vorliegt und [C] mit 70 Gew.-% der Konservierungszusammensetzung vorliegt.
  4. Die antimikrobielle Konservierungszusammensetzung nach Anspruch 1, wobei die Dreikomponenten-Konservierungszusammensetzung aus antimikrobiellen Mitteln für Körperpflegeformulierungen ein Gemisch umfasst aus
    [A] N-Undecylenoylmonoethanolamid,
    [B] N-Octanoylglycin, und
    [C] 2-Phenoxyethanol,
    wobei [A] mit 10 Gew.-%, [B] mit 7,5 Gew.-% und [C] mit 82,5 Gew.-% der Konservierungszusammensetzung vorliegt.
  5. Ein Verfahren zur Konservierung eines Körperpflegeprodukts vor mikrobiellem Befall, enthaltend eine wässrige Phase, umfassend die Dreikomponenten-Konservierungszusammensetzung nach Anspruch 1 mit 0,5 bis 2,5 Gew.-% der Körperpflegegesamtformulierung.
  6. Eine Körperpflegeformulierung zur topischen Anwendung, umfassend die antimikrobielle Konservierungszusammensetzung nach einem der Ansprüche 1 bis 5.
  7. Die Körperpflegeformulierung nach Anspruch 6, ausgewählt aus Lotionen, Cremes, Lösungen, Körperreinigungsmitteln, Shampoos, Seren, Wipes und Emulsionen.
  8. Die Körperpflegeformulierungen nach Anspruch 6, umfassend Körperpflegebestandteile, ausgewählt aus der Gruppe von Lösemitteln, oberflächenaktiven Substanzen, Emulgatoren, Rheologiemodifikatoren, Conditioner, Emollientien, Hautpflegebestandteilen und anderen Konservierungsmitteln, Verdickungsmitteln, Gleitmitteln, Füllstoffen, Antioxidantien, anderen Konservierungsmitteln, aktiven Bestandteilen, insbesondere dermatologisch aktiven Bestandteilen, Duftstoffen und dergleichen wie auch Gemischen davon.
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WO2015136546A1 (en) * 2014-03-10 2015-09-17 Galaxy Surfactants Ltd. Microemulsions of lipidated glycines and phenoxy ethanol for preservation of personal care products
WO2017141266A1 (en) * 2016-02-20 2017-08-24 Galaxy Surfactants Ltd. N-acyl sarcosines as antimicrobials for preservation of home and personal care products
DE102016104205A1 (de) * 2016-03-08 2017-09-14 Minasolve Germany Gmbh Wässrige Lösungen von N-Acyl-Aminosäuren
KR101665321B1 (ko) * 2016-04-27 2016-10-12 (주)네오팜 항노화용 조성물
GB201614087D0 (en) * 2016-08-17 2016-09-28 Byotrol Plc Anti-microbial composition
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